EP3861041A1 - Curable composition of low density - Google Patents

Abstract

The present invention relates to a moisture-curing composition comprising a) at least one moisture-reactive polymer P with a proportion of 10% to 60% by weight, based on the overall composition, b) at least one inorganic filler F with a proportion of at least 9% by weight, based on the overall composition, c) between 3% and 25% by weight, based on the overall composition, of at least one type of microscopic hollow beads H, characterized in that the composition has a density of less than 1.20 kg/l, preferably less than 1.10 kg/l, and the microscopic hollow beads H have a compressive strength, measured to ASTM D3102-72, of at least 2.5 MPa, preferably at least 5 MPa, and the microscopic hollow beads H have a volume-based particle size D90, measured by a Coulter counter, of less than 100 µm. The moisture-curing composition of the invention has good tensile strength coupled with high extensibility, good application properties with low expression forces, excellent pumping stability, and density stability after pump applications and in the case of prolonged storage, and is of very good suitability as an adhesive, sealant or coating material having low density for insulation applications or lightweight construction.

Description

 HARDENABLE COMPOSITION WITH LOW DENSITY

Technical field

 The invention relates to low-density moisture-curing compositions and their use as adhesives and sealants and coatings.

State of the art

 Moisture-curing compositions play an important role in many technical applications, for example as one- or two-component adhesives, sealants or coatings. Your curing is through

Crosslinking reactions, which take place under the influence of water via free or latent reactive groups such as isocyanate groups or silane groups, which react with themselves or with one another through contact with moisture, mainly from the air or as water in a second mixed component, and thus in the Composition included

Connect structural components covalently to a polymer network.

 Depending on the area of application, a very wide range of products with versatile individual properties can be formulated in the field of moisture-curing compositions. Additives play a major role, such as fillers, plasticizers, additives and

Adhesion promoters, which significantly influence the properties of the formulation, such as adhesion, mechanics and processability. Most of these moisture-curing compositions have a relatively high density, mostly in the range of 1.20 kg / L and above. The density is based on the one hand on the essential components such as moisture-reactive polymer, plasticizer and adhesion promoter additives, but the higher density above 1.00 kg / L is primarily on fillers. Fillers are usually indispensable in such moisture-curing compositions. On the one hand they ensure a significant reduction in the cost of the formulation, on the other hand they make a major contribution to the mechanical properties and the processing properties of the compositions. Unfortunately, common fillers such as chalk usually have a density in the range of over 2.00 kg / L, which is the total density of the

Composition significantly increased. In the course of progressing Light construction and to reduce transport costs, however, the longer the demand for more low-density adhesives and sealants in construction and industry. In particular, densities of 1.00 kg / L or even less are desired. To meet this need, microscopic hollow spheres have been used as additives in moisture-reactive for some time

Compositions used. These hollow spheres are essentially spherical, gas-filled particles with a diameter of at most 500 μm and shells, for example made of glass, silicates or

Plastics. These microscopic hollow spheres sometimes have a density of well below 1.00 kg / L and, when mixed into moisture-curing compositions, can significantly reduce the resulting overall density. In addition to the low density, this also enables advantageous properties such as thermal insulation or sound insulation

Realize what is desired in vehicle construction or floor adhesives, for example.

 However, the use of such microscopic hollow spheres leads to

Density reduction also has significant disadvantages. Especially that

Mechanical properties such as elongation at break and in particular the tensile strength suffer significantly when using such microscopic hollow spheres. This is especially a problem with structural adhesives, where excellent mechanics are absolutely essential. In order to counter this, large amounts of reinforcing carbon black have been mixed in as fillers. Although an acceptable mechanism and a reduced density can be achieved, the composition becomes extremely thick and can only be used

High-performance pumps or can be applied with heating. In addition, only deep black compositions can be produced in this way, which cannot be colored and are therefore aesthetically very limited

Have a wide range of applications.

 The use of microscopic hollow spheres with polymeric shells is also widespread, for example marketed under the trade name Expancel. Although these are very well compatible with the other components of the composition, they lead to the mechanics of the reduced weight

Compositions are preserved to a certain extent. However these hollow spheres are reversibly deformable under pressure, ie compressible. As a result, when the composition is squeezed out, for example from a cartridge, the composition runs out of the application device undesirably, which is extremely unpleasant for the user.

 In general, low-density moisture-curing compositions which contain hollow microscopic spheres have poor pumpability, and in many cases the density is irreversibly increased after pumping applications. In addition, most of these compositions have a reduced density which is not stable over time and which is irreversibly increased after prolonged storage. The reasons for this are, for example, destruction

substantial portions of the hollow spheres or in the immigration of substances into their cavities.

There is therefore still a need for a moisture-curing composition with a density of less than 1.20 kg / L, preferably less than 1.10 kg / L, in particular less than 1.00 kg / L, which does not have the above-mentioned disadvantages of the prior art and improves it Mechanics, especially tensile strength, good pumpability with low extrusion forces and a stable reduced density even after pump application and long storage.

Presentation of the invention

 It is therefore an object of the present invention to provide a moisture-curing composition with a density of less than 1.20 kg / L, preferably less than 1.10 kg / L, in particular less than 1.00 kg / L, which has improved tensile strength with good elongation at break, can be applied well at room temperature and is pumpable, the density of which is not irreversibly significantly increased by pumping or prolonged storage and which does not produce any run-on when applied.

This object is surprisingly achieved by a moisture-curing composition as described in claim 1. Through the use of an inorganic filler in combination with microscopic hollow spheres of a certain size and compressive strength and a defined amount of all components of the composition, a moisture-curing composition can low density are produced, which is the object of the present

Invention met.

 In preferred embodiments, both construction adhesives can

for example for floors, as well as comparatively easy to apply structural adhesives or sealants with sound and

Thermal insulation properties or fire-reducing properties.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

Ways of Carrying Out the Invention

 The invention relates to a moisture-curing composition comprising

 a) at least one moisture-reactive polymer P in a proportion of 10 to 60% by weight, based on the overall composition,

 b) at least one inorganic filler F, with a proportion of

 at least 9% by weight, based on the total composition, c) between 3 and 25% by weight, based on the total

 Composition, at least one type of microscopic flute balls H, characterized in that

 the composition has a density of less than 1.20 kg / L, preferably less than 1.10 kg / L, and

 the microscopic hollow spheres H have a compressive strength, measured according to ASTM D3102-72, of at least 2.5 MPa, preferably at least 5 MPa, and

 the microscopic hollow spheres H have a volume-based particle size D90, measured using a Coulter counter, of less than 100 pm.

The term “silane group” denotes a silyl group bonded to an organic radical with one to three, in particular two or three, hydrolyzable substituents on the silicon atom. Particularly common hydrolyzable

Substituents are alkoxy radicals. These silane groups are also called “Alkoxysilane groups” referred to. Silane groups can also be present in partially or fully hydrolyzed form.

 "Hydroxysilane", "isocyanatosilane", "aminosilane" and "mercaptosilane" are organoalkoxysilanes that are used in addition to the organic residue

Silane group have one or more hydroxyl, isocyanato, amino or mercapto groups.

 Substance names beginning with "poly" such as polyol or polyisocyanate refer to substances that formally contain two or more of the functional groups in their name per molecule.

 The term “organic polymer” encompasses a collective of chemically uniform macromolecules that differ in terms of degree of polymerization, molar mass and chain length, which was produced by a polyreaction (polymerization, polyaddition, polycondensation) and mostly has carbon atoms in the polymer backbone, as well as reaction products of such a collective of macromolecules.

 The term “polyurethane polymer” encompasses all polymers that are produced by the so-called diisocyanate polyaddition process. This also includes those polymers that are almost or completely free of urethane groups. Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyether polyureas, polyureas, polyester polyureas, polyisocyanurates and polycarbodiimides.

 Polymers containing silane groups are, on the one hand, silicone polymers

(Polydiorganosiloxane polymers) and, on the other hand, in particular organic polymers containing silane groups, which, usually and in particular in this document, are synonymous as “silane-functional polymers”,

 “Silane-modified polymers” (SMP) or “silane-terminated polymers” (STP) are referred to. Their networking takes place via the condensation of

Silanol groups with formation of siloxane bonds and is classically catalyzed by means of organotin compounds, such as in particular dialkyltin (IV) carboxylates.

The term “silane group-containing polyether” also includes silane group-containing organic polymers which, in addition to polyether units, can also contain urethane groups, urea groups or thiourethane groups. Such silane group-containing polyethers can also be referred to as “silane group-containing polyurethanes”.

In this document, “molecular weight” is understood to mean the molar mass (in grams per mole) of a molecule or part of a molecule, also referred to as the “residue”. The “average molecular weight” is the number average M _{n of} an oligomeric or polymeric mixture of molecules or residues

referred to, which is usually determined by means of gel permeation chromatography (GPC) against polystyrene as a standard.

 A substance or a composition is said to be "stable in storage" or "storable" if it can be stored at room temperature in a suitable container for a longer period of time, typically at least 3 months up to 6 months and more, without its application - or

Performance characteristics, especially the viscosity and the

Crosslinking speed, changed by the storage to an extent relevant to its use.

 A dashed line in the formulas in this document represents the bond between a substituent and the associated molecular residue.

A temperature of approx. 23 ° C is referred to as "room temperature".

 All industry standards mentioned in the document refer to the version valid at the time of filing the first application.

 The terms "mass" and "weight" are used synonymously in this document. A “percent by weight” (% by weight) denotes a percentage by mass which, unless stated otherwise, relates to the mass (weight) of the entire composition or, depending on the context of the entire molecule.

As a moisture-curing composition in the sense of this invention is in particular

a polyurethane composition, in particular a two-component system which crosslinks by reaction of polyols with isocyanates, such as is used for adhesives, coverings, casting compounds, sealing joints, moldings or block foams, or a one-component system with blocked (latent) isocyanate groups or blocked ( latent) Amino groups, such as those found in powder coatings, coil coatings,

 Electrocoating or liquid coating is used; or

- A composition based on silane-functional (silane group-containing) polymers. Compositions based on silane-functional polymers cure quickly even with a relatively low catalyst concentration and show good adhesive behavior (adhesion behavior) on many substrates even without the use of primers. They are also characterized by the lack of

 Isocyanates toxicologically advantageous.

For the purposes of this invention, therefore, suitable as moisture-reactive polymer P are preferably polyurethane polymers PU with free or latent isocyanates, and also silane-functional polymers STP.

The composition according to the invention contains the at least one moisture-reactive polymer P in a proportion of 10 to 60% by weight, preferably 15 to 50% by weight, based on the total composition.

In one embodiment, the moisture-reactive polymer P comprises at least one polyurethane polymer PU with free or latent isocyanate groups. As

Polyurethane polymers PU containing isocyanate groups are suitable for producing a composition according to the invention, for example polymers which are obtainable by reacting at least one polyol with at least one polyisocyanate, in particular a diisocyanate. This

The reaction can be carried out by reacting the polyol and the polyisocyanate using conventional methods, for example at temperatures from 50 ° C. to 100 ° C., optionally with the use of suitable catalysts, the polyisocyanate being metered in such a way that its

Isocyanate groups in relation to the hydroxyl groups of the polyol in

stoichiometric excess are present.

In particular, the excess polyisocyanate is chosen so that in the resulting polyurethane polymer, after the reaction of all the hydroxyl groups of the polyol, a free isocyanate group content of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, particularly preferably 0.3 to 2.5% by weight, based on the total polymer, remains.

 If necessary, the polyurethane polymer PU can also be produced using plasticizers, the plasticizers used not containing any groups that are reactive toward isocyanates.

 Polyurethane polymers with the stated content of free are preferred

Isocyanate groups resulting from the reaction of diisocyanates with

High molecular weight diols in an NCO: OH ratio of 1.3: 1 to 4: 1, in particular 1.5: 1 to 3: 1 and particularly preferably 1.7: 1 to 2.5: 1 can be obtained.

Suitable polyols for the production of the isocyanate group-containing polyurethane polymer are in particular polyether polyols, styrene-acrylonitrile-grafted polyether polyols, polyester polyols, polycarbonate polyols,

Poly (meth) acrylate polyols, polyhydroxy-functional fats and oils or

Polycarbonate polyols and mixtures of these polyols.

Particularly suitable polyether polyols, also called polyoxyalkylene polyols or oligoetherols, are those which contain polymerization products of

Ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized using a

Starter molecule with two or more active hydrogen atoms such as water, ammonia or compounds with several OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol,

Neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclophenol aol, hydrated 1, 1 - trimethylolethane, 1, 1, 1 -trimethylolpropane, glycerin, aniline, and mixtures of the compounds mentioned. Can be used both

Polyoxyalkylene polyols that have a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents

Unsaturation per gram of polyol (mEq / g), produced for example with the help of so-called double metal cyanide complex catalysts (DMC catalysts), and also polyoxyalkylene polyols with a higher one

Degree of unsaturation, produced for example with the help of anionic

Catalysts such as NaOH, KOH, CsOH or alkali alcoholates.

 Polyoxyethylene polyols and polyoxypropylene polyols, in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols, are particularly suitable.

 Particularly suitable are polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation lower than 0.02 meq / g and with a molecular weight in the range from 1Ό00 to 30Ό00 g / mol, and polyoxyethylene diols,

Polyoxyethylene triols, polyoxypropylene diols and polyoxypropylene triols with a molecular weight of 400 to 20Ό00 g / mol.

 So-called ethylene oxide-terminated (“EO-endcapped”, ethylene oxide-endcapped) polyoxypropylene polyols are also particularly suitable. The latter are special polyoxypropylene polyoxyethylene polyols which are obtained, for example, by using pure polyoxypropylene polyols, in particular

Polyoxypropylene diols and triols, after the polypropoxylation reaction has been completed, further alkoxylated with ethylene oxide and thus have primary hydroxyl groups. In this case, polyoxypropylene-polyoxyethylene diols and polyoxypropylene-polyoxyethylene triols are preferred.

Suitable polyester polyols are, in particular, polyesters which carry at least two hydroxyl groups and, by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with two or

polyhydric alcohols.

 Particularly suitable are polyester polyols which are prepared from dihydric to trihydric alcohols such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, glycerol, 1, 1, 1 -trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as, for example, succinic acid, glutaric acid, adipic acid,

Trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, Dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride or

Mixtures of the aforementioned acids, and polyester polyols from lactones such as e-caprolactone.

 Polyester diols are particularly suitable, in particular those which are prepared from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid,

Dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as

Dicarboxylic acid or from lactones such as e-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, dimer fatty acid diol and 1, 4-cyclohexanedimethanol as dihydric alcohol.

Particularly suitable as polycarbonate polyols are those as described by

Reaction, for example, of the abovementioned alcohols used to build up the polyester polyols with dialkyl carbonates such as dimethyl carbonate,

Diaryl carbonates such as diphenyl carbonate or phosgene are accessible. Polycarbonate diols, in particular amorphous polycarbonate diols, are particularly suitable.

Other suitable polyols are poly (meth) acrylate polyols.

Also suitable are polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil, or by chemical

Modification of so-called oleochemical polyols obtained from natural fats and oils, the epoxy polyesters or epoxy polyethers obtained, for example, by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols, or by hydroformylation and

Hydrogenation of unsaturated oils obtained polyols. Also suitable are polyols which are obtained from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimerization, of the degradation products or derivatives thereof obtained in this way. Suitable breakdown products of natural fats and oils are in particular fatty acids and fatty alcohols as well

Fatty acid esters, especially the methyl esters (FAME), which, for example can be derivatized by hydroformylation and hydrogenation to give hydroxy fatty acid esters.

Also suitable are polycarbonate polyols, too

Called oligohydrocarbonols, for example polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, as are produced, for example, by the company Kraton Polymers, USA, or polyhydroxy-functional copolymers from dienes such as 1,3-butadiene or

Diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols, for example those obtained by oxidation of polybutadiene or copolymerization of 1,3-butadiene and

Allyl alcohol can be produced and can also be hydrogenated.

 Also suitable are polyhydroxy-functional acrylonitrile / butadiene copolymers, such as those made from epoxides or amino alcohols and

carboxyl-terminated acrylonitrile / butadiene copolymers, which are commercially available under the name Hypro ^® CTBN from the company Emerald

Performance Materials, LLC, USA.

These polyols mentioned preferably have an average molecular weight of 250 to 30Ό00 g / mol, in particular 1 100 to 20Ό00 g / mol, and an average OH functionality in the range from 1.6 to 3.

Particularly suitable polyols are polyether polyols, in particular

Polyoxyethylene polyol, polyoxypropylene polyol and

Polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol,

Polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol,

Polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol.

In addition to these polyols mentioned, small amounts of

low molecular weight dihydric or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentylglycol, diethylene glycol,

Triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, Nonandiols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1, 1 -trimethylolethane, 1, 1, 1 - trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol Mannitol, sugars such as sucrose, other higher alcohols, low molecular weight alkoxylation products of the abovementioned dihydric and polyhydric alcohols, and also mixtures of the abovementioned alcohols are used in the preparation of the polyurethane polymer having terminal isocyanate groups.

Commercial polyisocyanates, in particular diisocyanates, can be used as polyisocyanates for the production of the polyurethane polymer. Examples of suitable diisocyanates are 1, 6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1, 5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate (TMDI), 1, 12 -Dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cydohexane

(= Isophorone diisocyanate or IPDI), perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1, 4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1, 3 and 1, 4 Bis (isocyanatomethyl) cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1, 3-xylylene diisocyanate, m- and p-tetramethyl-1, 4-xylylene diisocyanate, Bis- (1-isocyanato-1-methylethyl) naphthalene, 2,4- and 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI), 1,3 and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'- diisocyanatodiphenyl (TODI), oligomers and polymers of the aforementioned isocyanates, and any mixtures of the aforementioned isocyanates, MDI and TDI being particularly preferred.

In the composition according to the invention, the polyurethane polymer PU containing isocyanate groups is preferably in an amount of 10% by weight to 60% by weight, in particular in an amount of 15% by weight to 50% by weight, based on the overall composition. available. In one-component compositions containing the polyurethane polymer PU containing isocyanate groups, it may be advantageous to:

Block isocyanate groups and thus make latent to the

Increase storage stability by preventing premature reaction in the container.

 The blocking of isocyanate groups for the production of blocked or latent isocyanate groups by appropriate blocking agents, the

Being able to react thermo-reversibly with isocyanate groups is a common measure in the field and the person skilled in the art can easily carry it out. The person skilled in the art knows a wide number of suitable blocking agents or

Blocking groups, e.g. from the review articles by Douglas A. Wiek in Progress in Organic Coatings 36 (1999), 148-172 and in Progress in Organic Coatings 41 (2001), 1 -83, to which reference is hereby made.

 Another, sometimes even more advantageous method of stabilizing one-component polyurethane compositions is the use of latent hardeners. These are blocked (latent) polyamines, which are influenced by e.g. Water lose its blocking group and react to form free amines, which then react rapidly with the isocyanates with crosslinking.

 Such blocked amines as latent hardeners are also well known to the person skilled in the art and he finds many possibilities in the prior art for producing and using latent amines. For example, they are described in US 4,469,831, US 4,853,454 and US 5,087,661 and in EP 1772447, to which reference is hereby made.

In a further embodiment, the moisture-reactive polymer P comprises at least one silane-functional polymer STP.

In one embodiment thereof, the silane functional polymer is a

Polydiorganosiloxane polymer. So the composition is one

Silicone composition, which silane functional polymers with reactive

Silane end groups, for example alkoxy, acetoxy or oxime silane end groups and / or silane-functional polymers with silanol end groups, wherein In the latter case in particular, silicone crosslinkers must also be present in the composition. Such silicone systems have long been known to the person skilled in the art. For example, such silicone systems, in particular the associated silane-functional polymers and crosslinkers, as are suitable for the present invention, are described in WO 2018/033563 A1

described.

The silane-functional polymer STP is preferably a silane group-containing organic polymer, in particular a polyurethane, polyolefin, polyester, polyamide, poly (meth) acrylate or polyether or a mixed form of these polymers, each of which carries one or preferably more silane groups. The

Silane groups can be on the side of the chain or at the end and are bonded to the organic polymer via a carbon atom.

 The silane group-containing organic polymer is particularly preferably a polyurethane containing a silane group or a polyolefin containing a silane group or a polyester containing a silane group or a silane group containing

Poly (meth) acrylate or a silane group-containing polyether or a mixed form of these polymers.

 Most preferably, the silane group-containing organic polymer is a silane group-containing polyether or a silane group-containing polyurethane, which is preferably composed of polyether polyols.

The silane group-containing organic polymer preferably has alkoxysilane groups as silane groups, in particular alkoxysilane groups of the formula (I),

(f) x _(l)

- Si- (OR ¹⁴ ) _3.x

in which

R ^{14 represents} a linear or branched, monovalent hydrocarbon radical having 1 to 5 carbon atoms, in particular methyl or ethyl or isopropyl; R ^{15 represents} a linear or branched, monovalent hydrocarbon radical having 1 to 8 carbon atoms, in particular methyl or ethyl; and

x represents a value of 0 or 1 or 2, preferably 0 or 1, in particular 0. R ¹⁴ particularly preferably represents methyl or ethyl.

 Trimethoxysilane groups, dimethoxymethylsilane groups or triethoxysilane groups are particularly preferred.

 Here, methoxysilane groups have the advantage that they are particularly reactive, and ethoxysilane groups have the advantage that they are toxicologically advantageous and are particularly stable on storage.

The silane group-containing organic polymer preferably has an average of 1.3 to 4, in particular 1.5 to 3, particularly preferably 1.7 to 2.8, silane groups per

Molecule on. The silane groups are preferably terminal.

 The silane group-containing organic polymer STP preferably has an average molecular weight in the range from 1Ό00 to 30Ό00 g / mol, in particular from 2Ό00 to 20Ό00 g / mol. The silane group-containing organic polymer preferably has a silane equivalent weight of 300 to 25Ό00 g / eq, in particular 500 to 15Ό00 g / eq.

The silane group-containing organic polymer STP can be solid or liquid at room temperature. It is preferably liquid at room temperature.

Most preferably, the silane group-containing organic polymer STP is a silane group-containing polyether which is liquid at room temperature, the silane groups being in particular dialkoxysilane groups and / or trialoxysilane groups, particularly preferably trimethoxysilane groups or triethoxysilane groups.

Processes for the production of silanes containing polyethers are

Known specialist.

 In a preferred process, silane group-containing polyethers are obtainable from the reaction of allyl group-containing polyethers with hydrosilanes,

optionally with chain extension with, for example, diisocyanates.

In a further preferred process, silane group-containing polyethers are obtainable from the copolymerization of alkylene oxides and epoxysilanes, optionally with chain extension using, for example, diisocyanates. In a further preferred process, silane group-containing polyethers are obtainable from the reaction of polyether polyols with isocyanatosilanes, optionally with chain extension using diisocyanates.

 In a further preferred process, silane group-containing polyethers are obtainable from the reaction of polyethers containing isocyanate groups, in particular NCO-terminated urethane polyethers from the reaction of polyether polyols with an overstoichiometric amount of polyisocyanates, with aminosilanes, hydroxysilanes or mercaptosilanes. Polyethers containing silane groups from this process are particularly preferred. This process enables the use of a large number of commercially available, inexpensive starting materials, with which different polymer properties can be obtained, for example high extensibility, high strength, low elastic modulus, a low glass transition point or high weather resistance.

The polyurethane containing silane groups is particularly preferably obtainable from the reaction of NCO-terminated urethane polyethers with aminosilanes or hydroxysilanes. Suitable NCO-terminated urethane polyethers are obtainable from the reaction of polyether polyols, in particular polyoxyalkylene diols or polyoxyalkylene triols, preferably polyoxypropylene diols or polyoxypropylene triols, with an over-stoichiometric amount of polyisocyanates, in particular diisocyanates.

The reaction between the polyisocyanate and the polyether polyol is preferably carried out with exclusion of moisture at a temperature of 50 ° C. to 160 ° C., if appropriate in the presence of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups are in proportion to the hydroxyl groups of the polyol are present in a stoichiometric excess. In particular, the excess polyisocyanate is selected so that in the resulting urethane polyether, after the conversion of all hydroxyl groups, a free isocyanate group content of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight %, based on the total polymer, remains. Preferred diisocyanates are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate or IPDI), 2,4- and 2,6- Toluene diisocyanate and any mixtures of these isomers (TDI) and 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any mixtures of these isomers (MDI).

IPDI or TDI are particularly preferred. IPDI is most preferred. In this way, polyurethanes containing silane groups with particularly good light fastness are obtained.

Particularly suitable as polyether polyols are polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation lower than 0.02 mEq / g, in particular lower than 0.01 mEq / g, and an average molecular weight in the range from 400 to 25Ό00 g / mol, in particular 1000 to 20Ό00 g / mol.

 In addition to polyether polyols, other polyols can also be used proportionately, in particular polyacrylate polyols, as well as low molecular weight diols or triols.

Suitable aminosilanes for the reaction with an NCO-terminated urethane polyether are primary and secondary aminosilanes. Preferred are 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 4-amino-butyltrimethoxysilane, 4-amino-3-methylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-butyl-3-aminopropylanimyl, 3-aminopropylanimyl aminopropyltrimethoxysilane, adducts from primary aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and Michael acceptors such as acrylonitrile,

(Meth) acrylic acid esters, (meth) acrylic acid amides, maleic acid or fumaric acid diesters, citraconic acid diesters or itaconic acid diesters, in particular dimethyl or diethyl aminosuccinate, N- (3-trimethoxysilylpropyl).

Analogs of the aminosilanes mentioned with ethoxy or isopropoxy groups instead of the methoxy groups on the silicon are also suitable.

Suitable hydroxysilanes for the reaction with an NCO-terminated urethane polyether are in particular obtainable from the addition of aminosilanes to lactones or to cyclic carbonates or to lactides. Aminosilanes suitable for this purpose are in particular 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amino-3-methylbutyltrinnethoxysilane, 4-amino-3-methylbutyltriethoxysilane-4-aminobutyltriethoxysilane , 4-amino-3,3-dimethylbutyltriethoxysilane, 2-aminoethyltrimethoxysilane or 2-aminoethyltriethoxysilane.

3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane or 4-amino-3,3-dimethylbutyltriethoxysilane are particularly preferred.

 Suitable lactones are, in particular, g-valerolactone, g-octalactone, d-decalactone and e-decalactone, in particular g-valerolactone.

 Particularly suitable cyclic carbonates are 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2- on, 4-methyl-1, 3-dioxolan- 2-one or 4- (phenoxymethyl) -1, 3-dioxolan-2-one.

 Suitable lactides are in particular 1,4-dioxane-2,5-dione (lactide from 2-hydroxyacetic acid, also called “glycolide”), 3,6-dimethyl-1,4-dioxane-2,5-dione ( Lactide from lactic acid, also called “lactide”) and 3,6-diphenyl-1,4-dioxane-2,5-dione (lactide from mandelic acid).

 Preferred hydroxysilanes which are obtained in this way are N- (3-triethoxysilylpropyl) -2-hydroxypropanamide, N- (3-trimethoxysilylpropyl) -2-hydroxypropanamide, N- (3-triethoxysilylpropyl) -4-hydroxypentanamide, N - (3-Triethoxysilylpropyl) -4-hydroxyoctanamide, N- (3-triethoxysilylpropyl) -5-hydroxy-decanamide and N- (3-triethoxysilylpropyl) -2-hydroxypropylcarbamate.

Suitable hydroxysilanes are also obtainable from the addition of aminosilanes to epoxides or from the addition of amines to epoxysilanes.

Preferred hydroxysilanes obtained in this way are 2-morpholino-4 (5) - (2-trimethoxysilylethyl) cyclohexane-1-ol, 2-morpholino-4 (5) - (2-triethoxysilylethyl) cyclohexane-1 -ol or 1-morpholino-3- (3- (triethoxysilyl) propoxy) propan-2-ol.

Commercially available products are also suitable as silane group-containing polyethers or polyurethane, in particular the following: MS Polymer ™ (from Kaneka Corp .; in particular types S203H, S303H, S227, S810, MA903 and S943); MS Polymer ™ or Silyl ™ (from Kaneka Corp .; in particular the types SAT010, SAT030, SAT200, SAX350, SAX400, SAX725, MAX450, MAX951);

Excestar ^® (Asahi Glass Co. Ltd .; particular types S2410, S2420, S3430, S3630); SPUR + ^* (from Momentive Performance Materials; especially the types 101 OLM, 1015LM, 1050MM); Vorasil ™ (from Dow Chemical Co .; especially types 602 and 604); Desmoseal ^® (from Bayer MaterialScience AG; in particular the types S XP 2458, S XP 2636, S XP 2749, S XP 2774 and S XP 2821), TEGOPAC ^® (from Evonik Industries AG; in particular the types Seal 100, Bond 150, Bond 250), polymer ST (from Hanse Chemie AG / Evonik Industries AG, in particular types 47, 48, 61, 61 LV, 77, 80, 81); Geniosil ^® STP (from Wacker Chemie AG; in particular types E10, E15, E30, E35).

Particularly preferred silane group-containing organic polymers have end groups of the formula (II)

in which

R ^{16 stands} for a linear or branched, divalent hydrocarbon radical with 1 to 12 C atoms, which optionally has cyclic and / or aromatic components and optionally one or more heteroatoms, in particular one or more nitrogen atoms;

T for a divalent radical selected from -O-, -S-, -N (R ¹⁷ ) -,

-0-CO-N (R ¹⁷ ) -, -N (R ¹⁷ ) -CO-0- and -N (R ¹⁷ ) -CO-N (R ¹⁷ ) -,

wherein R ^{17 represents} a hydrogen radical or a linear or branched hydrocarbon radical having 1 to 20 carbon atoms, which optionally has cyclic components and which optionally has an alkoxysilane, ether or carboxylic acid ester group; and

R ¹⁴ , R ¹⁵ and x have the meanings already mentioned.

R ¹⁶ is preferably 1,3-propylene or 1,4-butylene, butylene being able to be substituted by one or two methyl groups.

R ¹⁶ particularly preferably represents 1,3-propylene. In a preferred embodiment of the moisture-curing composition according to the present invention, this comprises

Moisture-reactive polymer P at least one polyurethane polymer PU, the polyurethane polymer PU having free or latent isocyanate groups and the composition additionally optionally comprising a latent hardener for isocyanate groups.

In a further preferred embodiment of the moisture-curing composition according to the present invention, the moisture-reactive polymer P comprises at least one silane-functional polymer STP.

In the composition according to the invention, the silane-functional polymer STP is preferably in an amount of 10% by weight to 60% by weight, in particular in an amount of 15% by weight to 50% by weight, based on the total

Composition, present.

The composition according to the invention further comprises between 3 and 25% by weight, preferably between 4 and 20% by weight, based on the total

Composition of at least one type of microscopic hollow sphere H.

 The microscopic hollow spheres H have a compressive strength, measured according to ASTM D3102-72, of at least 2.5 MPa, preferably at least 5 MPa.

 The compressive strength can be determined using ASTM D3102-72. A detailed method for the measurement of preferred microscopic hollow spheres H based on this industrial standard can be found in WO 2012/033810, p. 15, second paragraph.

If microscopic hollow spheres H with a compressive strength of less than 2.5 MPa are used, not only is the pumpability and the density stability after pumping impaired, but surprisingly a material with lower tensile strength and poorer application properties is also obtained. It is therefore essential for the invention that microscopic hollow spheres H with a compressive strength of at least 2.5 MPa are used. Furthermore, the microscopic hollow spheres H to fulfill the

tasks according to the invention have a volume-based particle size D90, measured using a Coulter counter, of less than 100 pm. Other measurement methods such as sieve analysis or dynamic can also be used

Light scattering for the particle size can be used, however, it must be ensured (for example by comparative measurements) that any

method-dependent measurement errors are taken into account when comparing different methods. The Coulter counter has proven to be accurate and

reproducible measurement method for microscopic hollow spheres H, in particular those made of glass. Such a measurement, including a suitable measuring device, is described in US Pat. No. 8,261,577 (column 8, lines 7-12).

 The accuracy of the particle measurement with the Coulter counter of particles of this size, in comparison with other measurement methods, is described, for example, in the Journal of Geophysical Research, Vol. 115, C08024, 2010, pp. 1-19

described.

 The particle size D90 describes the value that 90% of the particles in a sample fall below. In other words, 90% of the particles of the microscopic hollow spheres H have a particle size of less than 100 pm.

The microscopic hollow spheres H preferably have a volume-based median particle size D50 of 15 to 65 pm and a volume-based particle size D10 of 5 to 30 pm.

 The median particle size D50 describes the value at which half of the particles in a sample are larger than this value and half of the particles are below this value. The particle size D10 describes the value at which 10% of the particles in a sample still have a size below this value.

The microscopic hollow spheres H preferably contain at most 5%, preferably at most 1%, particles with a particle size of more than 110 μm. In particular, the microscopic hollow spheres H do not contain a measurable amount of particles with a particle size of more than 110 pm. The microscopic hollow spheres H are essentially spherical bodies comprising a shell and gas in the interior. The gas can be, for example, air, CO2, nitrogen, oxygen, hydrogen, an inert gas or mixtures of these gases. The shell can for example be made of glass, in particular borosilicate glass, silicates, in particular aluminosilicate, or of polymers, in particular

thermoplastic polymers.

The microscopic hollow spheres H made of glass are preferred, in particular

Borosilicate glass. Suitable microscopic hollow spheres H made of glass and their production are taught, for example, in US Pat. Nos. 8,261, 577 and WO 2012/033810.

Preferred suitable, commercially available microscopic hollow spheres H made of glass are 3M ™ Glass Bubbles, available from 3M Deutschland GmbH. The types K20, K25, K32, K37 and S28HS are particularly preferred.

In a preferred embodiment, the moisture-curing

Composition according to the present invention, the microscopic hollow spheres H are hollow glass spheres, in particular borosilicate glass spheres, with a diameter of at most 110 μm.

The composition according to the invention further comprises at least one inorganic filler F, with a proportion of at least 9% by weight, based on the overall composition. The composition preferably contains at most 50% by weight, in particular at most 40% by weight, of inorganic filler F, based on the overall composition.

 A content of inorganic filler F of at least 9% by weight in

Combination with the microscopic hollow spheres H is essential for the mechanical properties as well as the application properties of the

cured composition. If the filler content is too high, above 50% by weight, it becomes difficult to set a sufficiently low density of less than 1.20 kg / L. Suitable inorganic fillers F are, for example, chalks, in particular natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearic acid, barite (heavy spar), talc, quartz powder, quartz sand, dolomites, ground cement, wollastonites, kaolins, calcined kaolins , Silicates such as mica (potassium aluminum silicate),

Molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, precipitated or pyrogenic silicas including highly disperse silicas from pyrolysis processes, metal powders such as aluminum, copper, iron, silver or steel, as well as metal oxides such as titanium dioxide.

Preferred fillers F are natural, ground or precipitated

Calcium carbonates, which optionally with fatty acids, in particular

Stearic acid, are coated, and precipitated or pyrogenic silicas including highly disperse silicas from pyrolysis processes, as well as metal oxides such as titanium dioxide and aluminum trihydrate, and mixtures of these fillers.

Aluminum trihydrate (ATFI), also called y-AI (OFI) 3 and known as mineral gibbsite (hydrargillite), is a flame-retardant filler known to the person skilled in the art. All fillers F can also be surface-coated, in particular

hydrophobic, present. Fatty acids are preferred as the surface coating, or alkylsilane-based coatings in the case of

Silica fillers. These form a hydrophobic shell around the particles. A particularly preferred fatty acid for coating is, for example, stearic acid.

In a preferred embodiment, the moisture-curing

Composition according to the present invention contains the

Composition at least 25% by weight of inorganic filler F, and preferably at most 40% by weight, based on the total composition. This embodiment has a particularly high tensile strength with a relatively low density and good squeezability and is very well suited as an adhesive or elastic sealant. In addition, this embodiment is white or colorful adjustable. A particularly preferred embodiment thereof comprises 25 to 40% by weight of inorganic filler F, based on the total Composition, as well as 4 to 20% by weight of microscopic hollow spheres H,

based on the total composition.

In a further preferred embodiment of the moisture-curing composition according to the present invention, the

Composition at least 9% by weight of inorganic filler F, and preferably at most 15% by weight, based on the total composition. This embodiment has a particularly low density with good

Tensile strength good squeezability and is as parquet adhesive or

Joint sealant very well suited. In addition, this embodiment is white or colorful adjustable. A particularly preferred embodiment thereof comprises 9 to 15% by weight of inorganic filler F, based on the total

Composition, and 5 to 15% by weight of microscopic hollow spheres H,

based on the total composition,

In further preferred embodiments, the moisture-curing

Composition according to the present invention contains the

Composition additionally at least one carbon black, preferably between 1 and 25 wt .-%, in particular between 5 and 20 wt .-%, carbon black, based on the total composition.

 The use of carbon black has the advantage that particularly good mechanical values, in particular tensile strength, and at the same time relatively low

Squeezing forces can be achieved, which in particular enables the use of these embodiments as structural adhesives. A particularly preferred embodiment of such carbon black-containing compositions comprises 9 to 15% by weight of inorganic filler F, based on the total composition, and 4 to 15% by weight of microscopic hollow spheres H,

based on the total composition,

Suitable blacks are all common industrial blacks, in particular dried blacks. All common industrial blacks (carbon black), such as ^Monarch® 570, available from Cabot, are suitable as dried blacks. In addition, other fillers such as organic fillers, for example PVC powder or graphite can be used. Expandable graphites which have an intumescent effect are preferred. All commercially available types are also suitable, such as Nyagraph ^® 250, available from Nyacol Nano Technologies or the expandable graphite from Asbury

Carbons.

After curing, preferred embodiments of the present invention achieve fire protection class C (s2, dO) according to DIN EN 13501-1.

The composition preferably contains at least one catalyst for crosslinking the moisture-crosslinking polymers P, in particular for crosslinking silane groups and / or for crosslinking isocyanate groups with amines or alcohols. Metal compounds and / or basic nitrogen or phosphorus compounds are particularly suitable as catalysts.

Suitable metal compounds are in particular compounds of tin, titanium, zirconium, aluminum or zinc, in particular diorganotin (IV) compounds such as in particular dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (IV) - dineodecanoate or dibutyltin ( IV) bis (acetylacetonate) and dioctyltin (IV) - dilaurate, as well as titanium (IV) - or zirconium (IV) - or aluminum (III) - or zinc (II) - complexes with in particular alkoxy, carboxylate, 1 , 3-diketonate, 1, 3-ketoesterate or 1, 3-ketoamidate ligands.

Titanium (IV) complex compounds are particularly suitable as organotitanate. The commercially available types Tyzor ^® AA, GBA, GBO, AA-75, AA-65, AA-105, DC, BEAT, BTP, TE, TnBT, KTM, TOT, TPT or IBAY (all from Dorf Ketal) are particularly suitable. ; Tytan PBT, TET, X85, TAA, ET, S2, S4 or S6 (all from Borica Company Ltd.) and Ken-React ^® KR ^® TTS, 7, 9QS, 12, 26S, 33DS,

38S, 39DS, 44, 134S, 138S, 133DS, 158FS or LICA ^® 44 (all from Kenrich Petrochemicals).

Suitable basic nitrogen or phosphorus compounds are in particular imidazoles, pyridines, phosphazene bases or, preferably, amines, hexahydrotriazines, biguanides, guanidines or amidines. Suitable amines are in particular alkyl, cycloalkyl or aralkylamines;

Amide-containing polyamines, polyamidoamines called as they are commercially available, for example under the brand name Versamid ^® (Cognis), Aradur ^® (Huntsman), Euretek ^® (Huntsman) or Beckopox® ^® (Cytec); or aminosilanes, such as in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -N'- [3- (trimethoxysilyl) propyl] ethylenediamine or their analogs with ethoxy groups instead of the methoxy groups on the silicon.

Suitable hexahydrotriazines are in particular 1,3,5-hexahydrotriazine or

1.3.5-Tris (3- (dimethylamino) propyl) hexahydrotriazine.

 Suitable biguanides are in particular biguanide, 1-butyl biguanide, 1, 1-dimethylbiguanide, 1-butylbiguanide, 1-phenylbiguanide or 1 - (o-tolyl) biguanide (OTBG). Suitable guanidines are in particular 1-butylguanidine, 1, 1-dimethylguanidine, 1, 3-dimethylguanidine, 1, 1, 3,3-tetramethylguanidine (TMG), 2- (3- (trimethoxysilyl) propyl) -1, 1, 3,3-tetramethylguanidine, 2- (3- (methyldimethoxysilyl) propyl) -1,1,3,3-tetramethylguanidine, 2- (3- (triethoxysilyl) propyl) -1,1,3,3-tetramethylguanidine , 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1, 5,7-tri-azabicyclo [4.4.0] dec-5-ene, 7-cyclohexyl- 1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1 - phenylguanidine, 1 - (o-tolyl) guanidine (OTG), 1, 3-diphenylguanidine, 1, 3-di (o-to- lyl) guanidine or 2-guanidinobenzimidazole.

 Suitable amidines are, in particular, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU),

1.5-diazabicyclo [4.3.0] non-5-ene (DBN), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1, 8-diazabicyclo [5.4 .0] undec-7-ene, N, N'-di-n-hexylacetamidine (DHA), 2-methyl-1, 4,5,6-tetrahydropyrimidine, 1, 2-dimethyl-1, 4,5,6 -tetrahydropyrimidine, 2,5,5-trimethyl-1, 4,5,6-tetrahydropyrimidine, N- (3-trimethoxysilylpropyl) -4,5-dihydroimidazole or N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole.

Furthermore, the composition can contain an acid as a cocatalyst, in particular a carboxylic acid. Aliphatic carboxylic acids such as formic acid, lauric acid, stearic acid, isostearic acid, oleic acid, 2-ethyl-2,5-dimethylcaproic acid, 2-ethylhexanoic acid, neodecanoic acid, aromatic are preferred Carboxylic acids such as salicylic acid, fatty acid mixtures from the saponification of natural fats and oils or di- and polycarboxylic acids, in particular poly (meth) acrylic acids.

The composition can contain further constituents, in particular the following auxiliaries and additives:

 - Flaft mediators and / or crosslinkers, especially aminosilanes such as in particular 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane , N- (2-aminoethyl) -N '- [3- (trimethoxysilyl) propyl] ethylenediamine or their analogs with ethoxy instead of methoxy groups, furthermore N-phenyl-, N-cyclohexyl- or N-alkylaminosilanes, Mercaptosilanes, epoxysilanes, (meth) acrylosilanes, anhydridosilanes, carbamosilanes, alkylsilanes or iminosilanes, oligomeric forms of these silanes, adducts of primary aminosilanes with epoxysilanes or (meth) acrylosilanes or anhydridosilanes, aminofunctional alkylsilsesofioxanesilanes, in particular aminosofunctional methylsilsesquioxanesilanes. Especially suitable are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-ureidopropyltrimethoxysilane, or Oligomeric forms of these silanes;

 - Drying agents, in particular tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or organoalkoxysilanes, which have a functional group in the a position to the silane group, in particular N- (methyldimethoxysilylmethyl) -0-methyl-carbamate, (methacryloxymethyl) silane, methoxy, methoxy, methoxy Orthoformic acid esters, calcium oxide or molecular sieves, in particular vinyltrimethoxysilane or vinyltriethoxysilane;

 Plasticizers, in particular carboxylic acid esters such as phthalates, in particular dioctyl phthalate, bis (2-ethylhexyl) phthalate, bis (3-propylheptyl) phthalate,

Diisononyl phthalate or diisodecyl phthalate, diesters of ortho-cyclohexanedicarboxylic acid, in particular diisononyl-1,2-cyclohexanedicarboxylate, adipates, in particular dioctyl adipate, bis (2-ethylhexyl) adipate, azelates, in particular bis (2-ethylhexyl) acelate, sebacate, in particular bis (2-ethylhexyl) sebacate or diisononyl sebacate, polyols, in particular polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, organic phosphorus or sulfonic acid esters, sulfonic acid amides, polybutenes or of natural fats or oils derived fatty acid methyl or ethyl esters, also called "biodiesel";

 - solvents;

 - organic fillers, in particular graphite, cellulose, polymer powder,

 in particular PVC powder;

 - Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

 - dyes and pigments;

 - Rheology modifiers, in particular thickeners, in particular

 Layered silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, pyrogenic silicas, cellulose ethers or hydrophobically modified polyoxyethylenes;

 - Stabilizers against oxidation, heat, light or UV radiation;

 - natural resins, fats or oils such as rosin, shellac, linseed oil, castor oil or soybean oil;

 - Non-reactive polymers, such as, in particular, homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular polyethylene (PE), polypropylene (PP ), Polyisobutylene,

 Ethylene vinyl acetate copolymers (EVA) or atactic poly-a-olefins (APAO);

- Surface-active substances, in particular wetting agents, leveling agents, deaerating agents or defoamers;

 - Biocides, especially algicides, fungicides or substances that inhibit fungal growth;

as well as others commonly used in curable compositions

Substances. It may be useful to dry certain ingredients chemically or physically before mixing them into the composition. In a preferred embodiment, the composition contains at least one additive, the additive being selected from the list consisting of

Plasticizers, curing catalysts, stabilizers, thixotropic agents, adhesion promoters and drying agents.

 In a particularly preferred embodiment, the composition contains at least one drying agent and at least one adhesion promoter.

The composition is preferably produced and stored in the absence of moisture. Typically, it is in a suitable packaging or arrangement, such as in particular a bottle, a can, a bag, a bucket, a barrel or a cartridge, to the exclusion of

Moisture stable in storage.

The composition can be in the form of a one-component or in the form of a multi-component, in particular two-component, composition.

 In the present document, “one-component” means a composition in which all components of the composition are stored mixed in the same container and which is curable with moisture.

 In the present document, “two-component” means a composition in which the components of the composition are present in two different components, which are separate from one another

Containers are stored. Only shortly before or during the application of the

Composition, the two components are mixed together, whereupon the mixed composition hardens, optionally under

Exposure to moisture.

A second or optionally further components are or are mixed with the first component before or during application, in particular via a static mixer or via a dynamic mixer.

The composition is applied in particular at ambient temperature, preferably in a temperature range between 0 ° C. and 45 ° C., in particular 5 ° C. to 35 ° C., and also cures under these conditions. In the case of application in the case of the use of silane-functional polymers STP, the crosslinking reaction of the silane groups begins, possibly under the influence of moisture. Existing silane groups can condense with existing silanol groups to siloxane groups (Si-O-Si groups). Existing silane groups can also hydrolyze to silanol groups (Si-OH groups) upon contact with moisture and through subsequent condensation reactions

Form siloxane groups (Si-O-Si groups). As a result of these reactions, the composition finally hardens.

 If water is required for the curing, this can either come from the air (atmospheric humidity), or the composition can be brought into contact with a water-containing component, for example by brushing, for example with a smoothing agent, or by spraying or it can be added to the composition during the application of water or a water-containing component, for example in the form of a

water-containing or water-releasing liquid or paste. A paste is particularly suitable in the event that the composition itself is in the form of a paste.

 In the case of curing by means of atmospheric moisture, the composition hardens from the outside inwards, a skin initially being formed on the surface of the composition. The so-called skin formation time is a measure of the curing speed of the composition. The speed of curing is generally determined by various factors, such as the availability of water, the temperature, etc.

The composition is suitable for a large number of applications, in particular as a resin for the production of fiber composites (composites), as rigid foam, flexible foam, molded part, elastomer, fiber, film or membrane, as a potting compound, sealant, adhesive, covering, coating or paint for construction and industrial applications, for example as seam sealing,

Cavity sealing, electrical insulation compound, filler compound, joint sealant, welding or flanged seam sealant, assembly adhesive, body adhesive, window adhesive, sandwich element adhesive, laminating adhesive, laminate adhesive, Packaging adhesive, wood adhesive, parquet adhesive, anchoring adhesive, flooring, floor coating, balcony coating, roof coating, concrete protective coating, parking garage coating, sealing,

Pipe coating, anti-corrosion coating, textile coating,

Damping element, sealing element or filler.

 The composition is particularly suitable as an adhesive and / or sealant, in particular for joint sealing and for elastic adhesive connections in construction and industrial applications, and as an elastic coating with crack-bridging properties, in particular for protecting and / or

Sealing for example roofs, floors, building icons, parking decks or

Concrete pipes, as well as an adhesive and / or sealant in the manufacture, repair and equipment of means of transport, such as rail transport, road transport, aircraft and ships.

 The composition thus preferably represents an adhesive or a sealant or a coating.

Such a composition typically contains plasticizers, fillers, adhesion promoters and / or crosslinking agents and drying agents and optionally other auxiliaries and additives.

The composition according to the invention has a density of less than 1.20 kg / L, preferably less than 1.10 kg / L. In particularly preferred

In embodiments, the composition according to the invention has a density of less than 1.00 kg / L, in particular less than 0.90 kg / L.

 The density can be determined by means of a density measuring device, preferably a pycnometer, or by means of water displacement (volume measurement using the Archimedes principle).

 The person skilled in the art can easily set the desired density of the composition by varying the amounts and type of the constituents of the composition according to the invention according to claim 1 by routine experiments.

For use as an adhesive or sealant, the composition preferably has a pasty consistency with pseudoplastic properties. On Such pasty sealant or adhesive is in particular from commercially available cartridges which are operated manually, by means of compressed air or battery, or from a barrel or hobbock by means of a feed pump or one

Extruder, optionally by means of an application robot, applied to a substrate.

 For use as a coating, the composition preferably has a consistency which is liquid at room temperature and has self-leveling properties. If necessary, it is slightly thixotropic, so that the coating can be applied to sloping to vertical surfaces without immediately flowing away. It is applied in particular by means of a roller or brush or by pouring and distributing using, for example, a roller, a scraper or a toothed trowel.

During application, the composition is preferably applied to at least one substrate.

 Suitable substrates are in particular

 - glass, glass ceramic, concrete, mortar, brick, brick, plaster or natural stones such as limestone, granite or marble;

 - Metals and alloys, such as aluminum, iron, steel or non-ferrous metals, as well as surface-coated metals or alloys, such as galvanized or chromed metals;

 - Leather, textiles, paper, wood, with resins, for example phenolic, melamine or epoxy resins, bound wood materials, resin-textile composites and other so-called polymer composites;

 - Plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA), epoxy resins, polyurethanes (PUR ),

Polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) or ethylene / propylene / diene terpolymers (EPDM), or fiber-reinforced plastics such as carbon fiber-reinforced plastics (CFRP ), Glass fiber reinforced plastics (GRP) or sheet molding compounds (SMC), where the plastics can preferably be surface-treated by means of plasma, corona or flame; coated substrates, such as powder-coated metals or alloys;

- Paints or varnishes, especially automotive top coats.

 If necessary, the substrates can be pretreated before the composition is applied, in particular by physical and / or chemical cleaning processes or by applying an adhesion promoter, an adhesion promoter solution or a primer.

Two identical or two different substrates, in particular the substrates mentioned above, can be glued or sealed.

After the composition has hardened with water, in particular in the form of atmospheric moisture, a hardened composition is obtained.

The use of the composition creates an article which has been glued, sealed or coated with the composition in particular. The article is in particular a building, in particular a building of civil engineering, an industrially manufactured good or a consumer good, in particular a window, a household machine or a

Means of transport such as in particular an automobile, a bus, a truck, a rail vehicle, a ship, an aircraft or a helicopter; or the article can be an attachment of it.

Another aspect of the invention is the use of a moisture-curing composition as described above as an adhesive, sealant or coating for sound insulation and / or thermal insulation.

Another aspect of the invention is the use of a moisture-curing composition as described in the foregoing as an adhesive, sealant or coating with fire protection properties, which after curing has achieved fire protection class C (s2, dO) in accordance with DIN EN 13501-1. Another aspect of the invention is the use of a moisture-curing composition as described above as an adhesive, sealant or coating for weight reduction.

Another aspect of the invention is a building or article of manufacture that has been glued, sealed or coated with an adhesive, sealant or a coating as described above.

Another aspect of the invention is a cured composition as described above.

Examples

 Exemplary embodiments are listed below which are intended to explain the described invention in more detail. Of course, the invention is not restricted to the exemplary embodiments described.

A “standard climate” is a temperature of 23 ± 1 ° C and a relative humidity of 50 ± 5%.

 The tensile strength and the elongation at break were according to DIN 53504

(Tensile speed: 200 mm / min) on films cured for 7 days at 23 ° C. and 50% relative atmospheric humidity with a layer thickness of 2 mm.

 To determine the squeezing force, the compositions were placed in internally coated aluminum cartridges (outside diameter 46.9 mm,

 Inside diameter 46.2 mm, length 215 mm, opening 15-M) filled and sealed airtight with a polyethylene plug (diameter 46.1 mm) from Novelis Deutschland GmbH. After conditioning for 24 hours at 23 ° C, the cartridges were opened and pressed out using a squeezer. For this, a nozzle with a 3 mm inner diameter opening was placed on the

Cartridge thread screwed on. The force required to press the composition at a pressing speed of 60 mm / min was determined using a pressing device (Zwick / Roell Z005). The specified value is an average of the forces, which after a squeeze distance of 22 mm, 24 mm, 26 mm and 28 mm was measured. The measurement was stopped after 30 mm of squeezing.

 The density of a sample was measured using a pycnometer with a volume of 100 ml at a temperature of 23 ° C.

 The theoretical density of a formulation was calculated using the raw material proportions and the density data of the raw materials.

 To determine the pump resistance, the density of a test formulation was first measured fresh after production, and a second time after an identical sample was conveyed through a barrel pump at a pressure of 30 bar (pressure peak during the metering stroke). A deviation of 5% or less of the two density measurements means satisfactory pump resistance.

The thread tension in mm describes the length of the sealant thread

Application of the sealant from an application gun remains when the nozzle is lifted from the applied sealant bead. A shorter thread is preferred.

Preparation of polymer P and thixotropic agent 1

Production of the silane-functional polymer STP-1

Excluding moisture, 1000 g of Acclaim ^® 12200 polyol (from Covestro; low monol polyoxypropylene diol, OH number 11.0 mg KOH / g, water content approx. 0.02% by weight), 43.6 g of isophorone diisocyanate (Vestanat ^® IPDI from Evonik Industries), 126.4 g of triethylene glycol bis (2-ethylhexanoate) (Solusolv ^® 2075 from Eastman Chem.) And 0.12 g of dibutyltin dilaurate are heated to 90 ° C. with constant stirring and kept at this temperature until the titrimetrically determined content of free isocyanate groups has a value of 0.63% by weight. -% had reached. Subsequently, 62.3 g of diethyl N- (3-trimethoxysilylpropyl) aminosuccinate (adduct of 3-aminopropyltrimethoxysilane and

Maleic acid diethyl ester; prepared according to the information in US Pat. No. 5,364,955) and the mixture was stirred at 90 ° C. until free isocyanate was no longer detected by FT-IR spectroscopy. The

silane functional polymer was cooled to room temperature and below

Exclusion of moisture kept. Preparation of the thixotropic agent 1

In a vacuum mixer, 1000 g hydrogenated diisononyl (Hexamol ^® DINCH, BASF) and 160 g of 4,4'-diisocyanate (Desmodur ^® 44, Germany MC L, Bayer MaterialScience AG) and heated gently. Then 90 g of monobutylamine were slowly added dropwise with vigorous stirring. The resulting white paste was further stirred for one hour under vacuum and cooling. The thixotropic agent 1 contains 20 parts by weight of this

 Reaction product and 80 parts by weight of diisodecyl phthalate. Preparation of moisture curing compositions

Comparative examples are marked in tables 2 to 5 with “(Ref.)”. The raw materials used are described in Table 1. Raw materials used

Table 1: Raw materials used in the example formulations.

Table 2: Compositions Z-1 to Z-4 in% by weight, in each case based on the total composition.

Table 3: Compositions Z-5 to Z-8 and Z-18 in% by weight, based in each case on the total composition “n / m” means that the value was not measured.

Table 4: Compositions Z-9 to Z-12 in% by weight, based in each case on the total composition “n / m” means that the value was not measured.

Table 5: Compositions Z-13 to Z-17 in% by weight, in each case based on the total composition. ^* heavy run-on when squeezing out of the cartridge at Z-17 Production of the STP compositions Z-1 to Z-18

 In a vacuum mixer, the silane-functional polymer STP-1, plasticizer and drying agent were mixed thoroughly for 5 minutes in accordance with the parts by weight given in Tables 2 to 5. The respective fillers, microscopic hollow spheres and thixotropic agents were then kneaded in at 60 ° C. for 15 minutes. With the heating switched off, adhesion promoter, catalyst and optionally stabilizer were then added and the mixture was processed under vacuum for 10 minutes to form a homogeneous paste. This was then filled into internally painted aluminum expansion piston cartridges and used again for the test specimens after storage. The exact quantities (in% by weight, based on the overall composition) of the individual raw materials for the respective tests are shown in Tables 2 to 5. The measurement results in Tables 2 to 5 clearly show that the

Compositions according to the invention are superior to the examples not according to the invention in terms of high tensile strength, low squeezing force, low thread tension, pump stability and consistently low density.

Claims

Claims

 1. A moisture curing composition comprising

 a) at least one moisture-reactive polymer P with a proportion of 10 to 60% by weight, based on the overall composition, b) at least one inorganic filler F, with a proportion of

 at least 9% by weight, based on the total composition, c) between 3 and 25% by weight, based on the total composition, of at least one type of microscopic flute spheres H,

 characterized in that the composition has a density of less than 1.20 kg / L, preferably less than 1.10 kg / L, and the microscopic flute balls Fl have a compressive strength, measured according to ASTM D3102-72, of at least 2.5 MPa, preferably at least 5 MPa , and the microscopic flute balls Fl have a volume-based particle size D90, measured with a Coulter counter, of less than 100 pm.

2. Moisture-curing composition according to claim 1, characterized in that the microscopic flute balls Fl are hollow glass balls with a diameter of at most 110 pm.

3. Moisture-curing composition according to claim 1 or 2, characterized in that the at least one inorganic filler F is selected from the list consisting of precipitated or ground chalk, precipitated or pyrogenic silica, titanium dioxide, and

 Combinations of these fillers.

4. Moisture-curing composition according to one of claims 1 to 3, characterized in that the moisture-reactive polymer P comprises at least one polyurethane polymer PU, wherein the

 Polyurethane polymer PU has free or latent isocyanate groups and the composition additionally optionally a latent FH hardener for

Includes isocyanate groups.

5. Moisture-curing composition according to one of claims 1 to 3, characterized in that the moisture-reactive polymer P comprises at least one silane-functional polymer STP.

6. Moisture-curing composition according to claim 5, characterized in that the silane-functional polymer STP has end groups of the formula (II),

 in which

R ^{14 represents} a linear or branched, monovalent hydrocarbon radical having 1 to 5 carbon atoms; R ^{15 represents} a linear or branched, monovalent hydrocarbon radical having 1 to 8 carbon atoms;

 x represents a value of 0 or 1 or 2;

R ^{16 is} a linear or branched, divalent hydrocarbon radical having 1 to 12 carbon atoms, which optionally contains cyclic and / or aromatic components and optionally one or more fleteroatoms,

 in particular has one or more nitrogen atoms; and

T for a divalent radical selected from -O-, -S-, -N (R ¹⁷ ) -,

-0-CO-N (R ¹⁷ ) -, -N (R ¹⁷ ) -CO-0- and -N (R ¹⁷ ) -CO-N (R ¹⁷ ) -, where R ^{17 is} a hydrogen radical or represents a linear or branched hydrocarbon radical having 1 to 20 carbon atoms, which optionally has cyclic components and which optionally has an alkoxysilane, ether or carboxylic acid ester group.

7. Moisture-curing composition according to one of claims 1 to 6, characterized in that the composition additionally comprises at least one additive, the additive being selected from the list consisting of plasticizers, curing catalysts, stabilizers, thixotropic agents, adhesion promoters and drying agents.

8. Moisture-curing composition according to one of claims 1 to 7, characterized in that the composition at least 25 % By weight of inorganic filler F, based on the overall composition.

9. Moisture-curing composition according to one of claims 1 to 7, characterized in that the composition additionally between 1 and 25 wt .-% carbon black, based on the

 Overall composition.

10. Moisture-curing composition according to one of claims 1 to 7, characterized in that the composition comprises 9 to 15% by weight of inorganic filler F, based on the entire composition, and 5 to 15% by weight of microscopic flute balls H, based on the entire composition.

11. Use of a moisture-curing composition according to one of claims 1 to 10 as an adhesive, sealant or coating for sound insulation and / or thermal insulation.

12. Use of a moisture-curing composition according to one of claims 1 to 10 as an adhesive, sealant or coating with fire protection properties, which reaches the fire protection class C (s2, dO) according to DIN EN 13501-1 after curing.

13. Use of a moisture-curing composition according to one of claims 1 to 10 as an adhesive, sealant or coating for weight reduction.

14. Building or article of manufacture that was glued, sealed or coated with an adhesive, sealant or a coating according to claim 13.

15. Cured composition according to one of claims 1 to 10.